Apparatus for manufacturing volatile chlorides



Nov. 29, 1932. R. A.1. MclNERNY ET AL 1,888,996

APPARATUS FOR MANUFACTURING VOLATILE CHLORIDES Filed March 19, 1928 2 Sheets-Sheet vlv ORNE Y0,

Nov. 29, 1932.

R. J. MCINERNY ET AL APPARATUS FCR MANUFACTURING VOLATILE CHLORIDES v 1928 2 Sheets-Sheet 2 Filed March 19,`

y 7 A TTORNE YE.

Patented Nov. 2&9, 1932 UNITED STATES PATENT oFFIcE Elura .1. MCINEBNY AND EUGENE E. WILLIAMS, or Los ANeEIEs, AND HERBERT E. i

eLAzE, or scorn rAsADENA, CALIFORNIA, AssIGNons, BY MEsNE AssIeNMENrs, ro rrINEnAnsINcnEMENr confirm, or WILMINGTON, DELAWARE, A coronA- 'rroN or DELAWARE APPARATUS FOB MANUFAUIUBING VOLATILE UHLORIDES VApplication filed Hatch 19, 1928. Serial No. 26Z,6l51t.v

The reaction between titanium dioxide and dry chlorine gas has been known for many years, and was mentioned by lRose und Wohler es early as 1850. 1t was found that the presence of carbon speeds up the reaction and ceuses it to proceed et a lower temperature then is possible with titanium dioxide alone.

@ne of the objects of our invention is to provide un improved method tor carrying out this reection in apparatus that is resistent to dry chlorine gas et high temperutures.

Another object of our invention is to elso provide means to 'separate the iron chloride which is formed during the reaction, iron being elweys present in some measure in the crude titanium dioxide used tor this purpose. llt is almost impossible to maire e perfect sepuretion oli this iron, but by our improve method und eppuretus smell emounts oi? iron urenot troublesome to hendle.

Another object oli our invention is to pro vide en eppuretus which is edapted to menun iecture volatile chlorides vother then titenium,

und which een else he edepted to eny renction where two products ure `ormed hothvef porous et the reaction temperature, but one of which condenses et e higher temperuture then the other. r j

ln order to fully explain our invention, we heve shown on the accompanying two sheets oi drawings, enepperetus which is precticnl for carrying out our improved method, which we will new describe. l

Figure 1 is e vertical, longitudinel sectionel view et un epperetus embodying our invention, teken on line l-1 of 'Figi d; Y

`Figure 2 is e iront end view or elevation oi seid epperetus; (J

Figure 3 is e vertical, transverse sectional view teken on line--S et Fig. 1 .und l 'Figure Il is e vertical,l transverse sectionel view telxen on line 4nd oi Fig. 1.

Referring now in detail to the drew/ings, 5 designates e furnace, heated with ges es at 6, with u tubular retort 7, made of cerborundum, hre clay, or any other suitable material which will resist chlorine et high tempereture, und closed et one end, es with e. removeble heed 8, having4 a. pyrometer 9, therethrough, and with a pipe 10, having perforaof seid iilter plete. A cover tions ,"inserted therethrough, said pipe being made of carborundum, tire clay or other suitable material, with means at 11, for connecting seid pipe 10 with a supply of chlorine.

Suitable stuliing boxes 12 and 13 are provided for said pyrometer and said perforated chlorine pipe 10. An outlet ue 1t, is shown forv said furnace. Seid retort 7 is pre'erubly extended through the end oi said furnace, and connects with u closed housmg 15, mede of cest iron or other resistant alloy, with connecting means, es et 16, with suitable pecking et 17. A pyrometer 18 is also inserted into seid, closed housing 15, through suitable stumng box 19.

lin the top of seid housing'lh, over en out-- d let is s, iilter plete 20, with asbestos pech`1 ing 21', er other suitable pecking, et the edges 22 is secured in piece over seid hlter plete 20, with en outlet 23 et one side with s pipe 24:, surrounded by u condenser wuter jiuchet 25, with inlet und outlet pipes, 26 end 27, respectively, Jlor supplying water thereto. in outer shell 28 is placed over seid closed housing 15, and provided with a. smoke steclx 29, 'trom the top thereof. Gas burners 30, 30, ere placed in seid shell, under seid closed housing 15.

.l receiver 31, is provided, connected with the pipe 24, seid receiver having e drew-od coclr 32. Connected with the top' of said receiver 31, is ereflux condenser pipe/33, with wuter jechet 34, with inlet and outlet pipes und 36, respectively.

Within the retort 7 is shown e quantity or" reaction mixture, designated 37. This cen be supplied to the open end of seidretort 7, after removing the door or wall 15, of the expansion chamber housing 15, by removing the bolts 38, 38.

The chlorine distribution pipes 10,10, per-u oruted on their under sides et 10, are covered with the reection mixture 37, that is, with e mixture of titanium dioxide and carbon, and the chlorine is thus introduced into said mixture. The expansion chamber 15 is heated and maintained et a point slightly above 136 C. so that the titaniumchloride is all kept thereof, said outlet connecting.

in a vaporous condition and is separated from the ferric chloride, which is a solid at this temperature. the reaction retort 7, through the pipes 10, under enough pressure (2 to 4 inches of Water) to cause the titanium tetrachloride to pass through the filter partition 20, together with the excess of chlorine present and also the carbon monoxide and carbon dioxide formed during the reaction of the chlorine upon the titanium dioxide and carbon. Ilhe receiver 31 for the lcondensed titanium tetrachloride is provided with a suitable water cooled condenser and the titanium tetra chloride is condensed therein and runs into the receiver as a liquid. A vent pipe 33 is provided on said receiver and a redux con. denser 34 is provided insaid ventv pipe to allow the escape of the unused chlorine and the carbon monoxide and carbon dioxide. but not the titanium tetrachloride, any of which might tend to pass over, is condensed in the reflux condenser and returned to the receiver 31. v

'lhe operation of the apparatus in carrying out our process ot-malzing titanium tetrachloride trom titanium dioxide, carbon and chlorine, may be briefly described as follows: A charge of previously mixed andy dried crude titanium dioxide and carbon is placed v in the retort 7, bv removing the door 15?,

which is then bolted. Water is turned on to run through the condenser jackets 25 and 34. -Gas burners 6 and 30 are lighted. 'lhc retort 7 and its charge 37 is brought to a' dull 'red heat at about 600 C. and dry chlorine is turned in through the pipes 10, 11, which percolates slowly through the charge 37. ril`he chlorine. acts on the titanium dioxide, forming titanium tetrachloride and releasing` oxygen which combines with the carbon vin the charge forming carbon dioxide and carbon monoxide, the titanium tetrachloride being a vapor at 600 C. is carried out into expansion chamber '15 with the excess chlorine, carbon monoxide and carbon dioxide and anv ferrie chloride which may be formed from the iron contained in the crude titanium dioxide used in the charge 37. Expansion chamber 15 is maintained at a temperature of 136 C.

which is the volatilization temperature of ti-v tanium tetrachloride. and the ferrie chloride chloride.

lis deposited therein but the titanium tetrachloride remains behind. Filter plate 20 and f filter plate cover 22, are. also kept at a tem-y perature of 136 C. and the titanium tetrachloride being still in the gaseous phase passes into the condenser tube 24 and is cooled by the water jacket 25, and in condensed formV rlFhe chlorine is forced into runs into the receiver 31, from which it is drawn od through the cock 32. The unused chlorine mixture withcarbon monoxide and carbon dioxide passes into the condenser tube 33, cooled by the water jacket 34, and any titanium tetrachloride not condensed in 24 is condensed in 33 and runs back to receiver 31. 'lhe unused chlorine mixed with carbon monoxide and carbon dioxide passes out of pipe 33 and may be further treated to recover the unused chlorine.

After a charge has become exhausted in the retort 7, the door 15a is opened and the residue in the retort 7 is scraped out into expansion chamber 15 and is removed with any ferrie chloride which may have been deposited in the expansion chamber 15.

The lilter plate 20 is made of filtros (a Sorous silica composition), porous carborunum or alundum or any other porous iltering medium which is resistant to chlorine, titanium tetrachloride, or iron chloride at 136 C.

We are aware that many changes in the general construction and arrangement of our y apparatus as hene shown for descriptive and illustrative purposes can be made and We do not, therefore, limit our invention to the details of the showing thus made, except as we mav be limited by the hereto appended claims.

We claim: 1. lln an apparatus for the purposes referred to', in combination, a retort, means for heating the same, an expansion chamber in communication therewith, means for heating the sam-e, a heated filter diaphragm covering an outlet from said expansion chamber, a receiver connected with said expansion chamber outside of said filter diaphragm, means for cooling and condensing matter passing to said receiver, and a reflux condenser connected with said receiver, with means for cooling the same.

2. ln an apparatus for th-e purposes referred to. in combination` a retort, means for heating the same to a desired temperature, means .for introducing material to be acted upon to said retort, means for introducing a reaction gas into said material, means providing a closed expansion chamber with which said retort communicates with a sealed connection therebetween, means for heating said expansion chamber to a desired temperature. a condenser with which said expansion chamber connects,means interposed between said expansion chamber and said condenser for separating solid matter from gaseous product, and a receiver connected with said condenser to receive condensed product Y vconnection therebetween, a liquid receiver, a

condenser connecting` said expansion chamber and said liquid receiver, with closed connections therebetween, and a filter means between said expansion chamber. and said condenser. y Signed at Los Angeles, Los Angeles County, California., this 9th day of March, 1928.

RALPH J MCINERNY. EUGENE F. WILLIAMS. HERBERT L. GLAZE. 

